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US-12617800-B2 - Renewable monomer and polymer thereof

US12617800B2US 12617800 B2US12617800 B2US 12617800B2US-12617800-B2

Abstract

Described is a compound having the structure (I), (II) or (V), Formulae (I), (II), (V), wherein R 1 is —H, —CH 2 OH or —CH(OH)CH 2 OH; R 2 is —H, —OH, or —CH 2 OH; R 3 is —H, —OH, or —CH 2 OH; n is 0 or 1; p is 0 or 1; R 10 is hydrogen or a hydrocarbon moiety with 1 to 20 carbon atoms, wherein each hydrogen atom of the hydrocarbon moiety may optionally be substituted with a C 1 -C 4 -alkyl group or a halogen atom; R is either —Z—F or Y and wherein Z is a hydrocarbon moiety with 0 to 10 carbon atoms, optionally substituted with 1 to 4 C1-C4-alkyl groups or 1 to 4 halogen atoms, and F is —COOH, —CH(COOH) 2 , —COOR 4 , —CHO, —CH(CHO) 2 , —C 2 H 3 , —C 2 H, —N 3 , —NH 2 , —NHR 7 , —OH, —CH(CH 2 OH) 2 , wherein R 4 is a C 1 -C 4 -alkyl group and R 7 is a C 1 -C 4 -alkyl group and wherein Y is hydrogen or a linear, branched or cyclic organic residue having 1 to 20 carbon atoms with the proviso that if R is Y and n is 0 at least one of R 1 or R 2 is not hydrogen. Also described is a method for the preparation of the compound, a polymer derived from the compound as well as a method for the preparation of the polymer.

Inventors

  • Jeremy Luterbacher
  • Lorenz MANKER
  • Graham Dick
  • Stefania BERTELLA

Assignees

  • Ecole polytechnique fédérale de Lausanne (EPFL)

Dates

Publication Date
20260505
Application Date
20201014
Priority Date
20191014

Claims (14)

  1. 1 . A compound having the structure (I) wherein R 1 is —H, —CH 2 OH or —CH(OH)CH 2 OH; R 2 is —H, —OH, or —CH 2 OH; n is 0 or 1; R is either —Z—F or Y, and wherein Z is a hydrocarbon moiety with 0 to 10 carbon atoms, optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms, and F is —COOH, —CH(COOH) 2 , —COOR 4 , —CHO, —CH(CHO) 2 , —C 2 H 3 , —C 2 H, —N 3 , —NH 2 , —NHR 7 , —OH, —CH(CH 2 OH) 2 , and Y is hydrogen or a linear, branched or cyclic organic residue having 1 to 20 carbon atoms wherein R 4 is a C 1 -C 4 -alkyl group; R 7 is a C 1 -C 4 -alkyl group, with the proviso that if R is Y and n is 0 at least one of R 1 or R 2 is not hydrogen.
  2. 2 . The compound according to claim 1 , wherein R is —Z—F, wherein Z is a hydrocarbon moiety with 0 to 10 carbon atoms, optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms, and F is —COOH, —CH(COOH) 2 , —COOR 4 , —CHO, —CH(CHO) 2 , —C 2 H 3 , —C 2 H, —N 3 , —NH 2 , —NHR 7 , —OH, or —CH(CH 2 OH) 2 .
  3. 3 . The compound according to claim 1 , wherein R is —(CH 2 ) m COOH; —(CH 2 ) m CH(COOH) 2 ; —(CH 2 ) m COOR 4 ; —(CH 2 ) m CH(COOR 4 ) 2 ; —(CH 2 ) m CHO; —(CH 2 ) m CH(CHO) 2 ; —(CH 2 ) m C 2 H 3 ; —(CH 2 ) m CH(C 2 H 3 ) 2 ; —(CH 2 ) m C 2 H; —(CH 2 ) m N 3 ; —(CH 2 ) m NH 2 ; —(CH 2 ) m CH (NH 2 ) 2 ; —(CH 2 ) m NHR 7 ; —(CH 2 ) m CH (NHR 7 ) 2 ; —(CH 2 ) m OH; or —(CH 2 ) m CH(CH 2 OH) 2 , where m is an integer from 0 to 10.
  4. 4 . The compound according to claim 1 , wherein R is —C 6 H 4 COOH, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 COOR 4 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 COOR 4 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 CHO, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 CHO, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 C 2 H 3 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 C 2 H 3 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 C 2 H, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 C 2 H, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 N 3 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 N 3 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 NH 2 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 NH 2 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 NHR 7 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; —C 6 H 10 NHR 7 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 4 OH, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups or 1 to 4 halogen atoms; or —C 6 H 10 OH, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups.
  5. 5 . The compound according to claim 1 , wherein n is 0 and R 2 is —H.
  6. 6 . The compound according to claim 1 , wherein R is: —(CH 2 ) m COOR 4 ; —C 6 H 4 COOR 4 , wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; —C 6 H 10 COOR 4 , wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; or —(CH 2 ) m CH(COOR 4 ) 2 ; wherein m is 0 to 4, and R 4 is a C 1 -C 4 -alkyl group.
  7. 7 . The compound according to claim 1 , wherein the compound has the structure (I), and wherein n is 0.
  8. 8 . The compound according to claim 1 , wherein Y is a linear or branched organic residue with 1 to 10 carbon atoms.
  9. 9 . A method for preparing a compound according to claim 1 having the structure (I): said method comprising the steps of a. providing a carbohydrate or a lignocellulose-containing composition; b. adding an aldehyde optionally comprising at least one functional group selected from the group consisting of carboxylic acid, carboxylic amide, ether, alkyne, alkene, aldehyde, chloride, hydroxyl, azide, carboxylic acid ester, aldehyde, vinyl, and amine to the carbohydrate or to the lignocellulose-containing composition to obtain a mixture; c. heating the mixture under acidic conditions; and d. separating, the compound.
  10. 10 . The method according to claim 9 , wherein the aldehyde of step b) is selected from a group consisting of acetaldehyde, propionaldehyde, isobutyraldehyde, glyoxylic acid, dialdehyde, cyclopropanecarboxaldehyde, isobutyraldehyde, pivaldehyde, tolualdehyde, and benzaldehyde.
  11. 11 . The method according to claim 9 , wherein the carbohydrate or lignocellulose-containing composition is an aldopentose, an aldohexose, an aldoheptose, a ketohexose, a ketoheptose, a lignocellulose-containing composition having a lignin content of 20 to 40 wt. %, based on the total weight of the lignocellulose-containing composition, or a mixture thereof.
  12. 12 . The method according to claim 9 , wherein the aldehyde has the formula: CHO—(CH 2 ) m COOH; CHO—C 6 H 4 COOH, wherein the aromatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; CHO—C 6 H 10 COOH, wherein the aliphatic ring is optionally substituted with 1 to 4 C 1 -C 4 -alkyl groups; or CHO—(CH 2 ) m CH(COOH) 2 , and wherein the method comprises the additional step of adding a C 1 -C 4 -alkylalcohol after step c. and before step d.
  13. 13 . The method according to claim 9 , wherein the mixture is heated at 60 to 110° C., and/or wherein the heating is conducted at a pressure of 80 to 120 mbar.
  14. 14 . The method according to claim 9 , wherein step a. comprises providing a lignocellulose-containing composition, wherein the lignocellulose-containing composition is a lignocellulosic biomass.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a U.S. National Stage Application filed under 35 U.S.C. § 371 of International Application No. PCT/EP2020/078874, filed Oct. 14, 2020, which claims the benefit of European Application No. 19 203 000.5, filed Oct. 14, 2019. Both of these applications are hereby incorporated by reference in their entireties. BACKGROUND Plastic has become a ubiquitous consumable in our daily lives. Global plastic production has increased to over 380 million tons per year in 2015 with a compound annual growth rate of 8.5%. Global life-cycle greenhouse gas emissions from production of these plastics were 1.7 Gt of CO2-equivallent (CO2e) in 2015, or 5% of total global greenhouse gas emissions, and is estimated to increase to 6.5 Gt CO2e by 2050 if current trends continue (Zheng, J. & Suh, S. Strategies to reduce the global carbon footprint of plastics. Nat. Clim. Chang. 9, 374-378 (2019). Also, more than a third of this plastic has an average lifetime of less than six months before it is discarded—the majority of which ends up in landfills or the environment (Geyer, R.; Jambeck, J. R.; Law, K. L. Production, Use, and Fate of All Plastics Ever Made. Sci. Adv. 2017, 3 (7), e1700782). Not only are plastics produced from non-renewable and polluting fossil fuels, but they are also non-biodegradable and detrimental to the world's ecosystems. To mitigate emissions and pollution from plastic production, research into biobased and biodegradable polymers is sorely needed. In 2018, 2.274 million tons of bioplastic were produced—amounting to less than 1% of global plastic production. Of this 2.274 million tons, 38.7% consists of biodegradable polymers. However, with increasing consumer demand for renewable products, the bioplastics market is expected to expand considerably in the next decade (Biopolymers facts and statistics 2017 report. Institute for Bioplastics and Biocomposites). Polymers from renewable resources have been developed, but usually their mechanical properties and/or their processability come short of the properties of petroleum-based plastics. The frequently used polymers from renewable resources polylactic acid (PLA), polybutyl succinate (PBS), polyhydroxyalkonates (PHA) are not suitable replacements for packaging materials such as polyethylene terephthalate (PET), the most abundant polyester, which comprises 8% of the global polymer market (Munõz-Guerra, S.; Lavilla, C.; Japu, C.; Martínez de Ilarduya, A. Renewable Terephthalate Polyesters from Carbohydrate-Based Bicyclic Monomers. Green Chem. 2014, 16 (4), 1716-1739). This is due to their inferior mechanical properties and processability. Coca-Cola co. and DuPont have commercialized partially renewable PET through the use of renewably derived diols but still have not managed to find a renewable route to economically produce or replace the rigid diacid component, terephthalic acid (TPA). A satisfying renewable replacement for PET has not been found yet. At the moment, the most promising sustainable replacement candidate for PET appears to be poly(ethylene furanoate) (PEF), which is manufactured from 2,5-furandicarboxylic acid. While PEF may be manufactured from renewable resources, the multi-step reaction sequence from glucose, combined with undesirable degradation products and the intensive separations required prior to polymerization, have limited its commercialization. Furthermore, there have been reports that PEF is non-biodegradable (Sajid et al., Green Chem. 2018, 20 (24), 5427-5453). Renewable polyesters have been prepared using dianhydrohexitols, such as the commercially available isosorbide, which are rigid, bicyclic diols derived from sugars. Polyesters containing these cyclic sugars also have good thermal and mechanical properties and show improved biodegradability (Zamora, F.; Hakkou, K.; Muñoz-Guerra, S.; Galbis, J. A. Hydrolytic Degradation of Carbohydrate-Based Aromatic Homo- and Co-Polyesters Analogous to PET and PEI. Polymer Degradation and Stability 2006, 91 (11), 2654-2659). However, the major drawback of these sugars is their low reactivity—caused by the secondary nature of the alcohol groups, and in some cases, the different steric orientations of the hydroxyl groups with respect to the fused rings. In addition, isosorbide is normally obtained by acid catalyzed dehydration of the D-sorbitol. In order to obtain the required purity of the isosorbide monomer, laborious reaction steps including distillation, recrystallization from alcohols, recrystallization from the melt, or a combination of these methods are required. In addition, the synthesis is limited to the diol, and the manufacture of derivatives such as amines requires further synthetic steps. A similar bicyclic, sugar-derived, diacid (2,3:4,5-di-O-methylene-galactarate) has also been synthesized via acetalization of galactaric acid with formaldehyde in an attempt to directly replace terephthalic acid (TPA). Although high molecular weight